Systematic physical and electrochemical characterizations revealed unique positive multifunction of a polymeric salen-type nickel(II) complex, poly[Ni(CH 3salen)], as an additive for conventional cathodes in lithiumion batteries. Due to its promising electrochemical and mechanical properties, combined with its unique threedimensional weblike electron-network structure, the redoxactive-organometallic polymer can eliminate conductive carbon and replace a significant portion of the poly(vinylidene fluoride) (PVdF) binder that has been used in conventional LiFePO 4 cathodes. By replacing such electrochemically inactive components (i.e., carbon and PVdF), LiFePO 4 cathodes with poly[Ni(CH 3 -salen)] deliver improved energy density compared with the conventional LiFePO 4 cathode. Facile electron transfer via large-area contact at polymer/LiFePO 4 interfaces significantly accelerates charge-transfer reactions and consequently improves the rate capability of the cathodes. In addition, unlike PVdF, poly[Ni(CH 3 -salen)] retains steady Young's modulus values after immersing in an electrolyte solvent, which enhances the mechanical integrity of the cathodes during the cycling of battery cells and thereby improves their cycle life. The unique multifunction of the poly[Ni(CH 3 -salen)] will be of broad interest for its application in next-generation energy-storage devices.

High-voltage LiNi0.5Mn1.5O4 (LNMO) spinel offers high specific energy and good rate capability with relatively low raw-material cost due to cobalt-free and manganese-rich chemical compositions. Also, increasing mass loading (mg/cm2) by thickening cathodes has been one of the focused areas to greatly improve the energy density of lithium-ion batteries (LIBs) at the cell level. The LNMO cathode made with a polyvinylidene fluoride (PVdF) binder, however, suffers from an oxidative decomposition of liquid electrolytes and cathode delamination from a current collector. This problem is exacerbated with an increase in thickness. In this study, we developed a lithium polyacrylate (LiPAA)–sodium alginate (Na-Alg) composite binder series that offer positive multifunctions such as enhancing cathode adhesion and cohesion, improving cycle life, creating an effective passivating layer at the cathode–electrolyte interface (CEI), and lowering cell impedance. Comprehensive design of systematic experiments revealed a close chemo-mechano-electrochemical relationship in the thick high-voltage cathodes. Among the various binder compositions, the LiPAA (30 wt %)–Na-Alg (70 wt %) binder offered a strong adhesion property and positive multifunctions at the CEI layer, which consequently stabilized the solid-electrolyte interfacial (SEI) layer on the graphite anode and improved LIB performances. This novel composite binder will be applicable to various types of thick cathodes in future studies.

Chemical composition – moisture sensitivity relationship of LiNixMnyCo1-x-yO2 (NMC) cathode materials was investigated by exploring crystal structures, surface properties and electrochemical performance behaviors of various commercial NMC powders: LiNi1/3Mn1/3Co1/3O2 (NMC111), LiNi0.5Mn0.3Co0.2O2 (NMC532), LiNi0.6Mn0.2Co0.2O2 (NMC622), and LiNi0.8Mn0.1Co0.1O2 (NMC811). The NMC powders were stored in different moisture conditions: moisture-free, humidified air, or immersed in water. Rietveld refinement analysis of X-ray diffraction (XRD) data and scanning electron microscopy (SEM) were used to characterize the crystal structure changes and the evolution of particle surfaces morphologies. The effect of moisture contamination on the electrochemical properties of NMC cathodes were studied by galvanostatic cycling and electrochemical impedance spectroscopy (EIS). The moisture contamination resulted in either structural disorder or unwanted surficial deposition products, which increased a charge-transfer impedance and consequent performance degradation of battery cells. The results showed that NMC's moisture vulnerability increased with Ni content (x) despite protective coatings on commercial particles, which stressed the necessity of alternative surface passivation strategies of Ni-rich NMC for broad applications such as electric vehicles (EVs) and electrified aircraft propulsion (EAP).